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WO2017041185A1 - Recyclage de batteries - Google Patents

Recyclage de batteries Download PDF

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Publication number
WO2017041185A1
WO2017041185A1 PCT/CA2016/051073 CA2016051073W WO2017041185A1 WO 2017041185 A1 WO2017041185 A1 WO 2017041185A1 CA 2016051073 W CA2016051073 W CA 2016051073W WO 2017041185 A1 WO2017041185 A1 WO 2017041185A1
Authority
WO
WIPO (PCT)
Prior art keywords
feedstock
granulated
batteries
size
preheating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CA2016/051073
Other languages
English (en)
Inventor
Wayne Stevens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Marlie Inc
Original Assignee
Marlie Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Marlie Inc filed Critical Marlie Inc
Publication of WO2017041185A1 publication Critical patent/WO2017041185A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a system and process for recycling sealed cell batteries.
  • a known method for recycling alkaline batteries involves mechanically removing the casing from the battery cell and then using chemical processes to separate the solid materials of the cell.
  • Major solid components of the cells are carbon, zinc, potassium, and manganese.
  • chemical separation processes There are several problems with chemical separation processes. Firstly, the component materials involved are of low value while chemical processing is expensive. Also, additional waste streams are created with the chemical processes. In view of these drawbacks, this recycling method has not found widespread use.
  • a method of reclaiming constituent components of a feedstock of sealed batteries including: a) granulating the batteries to form a granulated feedstock; b) preheating the feedstock by agglomerating granulated feedstock to promote a spontaneous exothermic reaction within the agglomerate thereby self-heating the feedstock; c) further heating the preheated feedstock with an external heat source to complete drying of the feedstock; d) screen separating the dried feedstock into a coarse fraction and a powder fraction.
  • the agglomeration is a batch process wherein granulated feedstock is placed in containers for a preselected amount of time.
  • agglomeration can be a continuous process wherein granulated feedstock is fed into a moving container, such as a conveyor with upright sidewalls, for a preselected amount of time.
  • the feedstock is heated to between 200 and 800°F.
  • the feedstock is pre-heated for at least 20 minutes.
  • waste heat from the preheating step is collected and used as an external heat source when further heating the preheated feedstock.
  • the batteries are granulated to a size not larger than 1 3/4 inches.
  • step b') Preferably further including the step b') after step b) as follows: b') further shredding the material to a size not exceeding 3/4" in size.
  • the coarse fraction comprises a magnetic portion and a non-magnetic portion.
  • the sealed batteries are alkaline batteries containing mercury wherein mercury vapour is extracted during the preheating step.
  • the powder fraction comprises zinc oxide, manganese dioxide, and potassium hydroxide.
  • the further heating is carried out by transferring the feedstock onto moving conveyors.
  • radiant heating is used to heat the feedstock on the moving conveyors.
  • waste heat from the preheating step is collected from the air drawn through the feedstock and used as an external heat source when further heating the preheated feedstock.
  • the screen separating of the dried feedstock into a coarse fraction and a powder fraction is carried out in a rotex screener.
  • FIG. 1 is a flow diagram of the method for battery recycling in accordance with this invention.
  • Figure 2 is a schematic diagram showing the method of battery recycling described in Figure 1,
  • Figure 3 is a flow diagram showing the flow of material and energy within the de-gas station and further how energy is reclaimed and re-used outside of the degas station.
  • Figure 4 is a chart indicating possible reactions occurring during the preheating/de-gassing stage.
  • a battery is a series of battery cells.
  • a 9 V battery is a true battery
  • AAA through D size batteries are cells.
  • the term battery is used to mean either true batteries or cells.
  • Alkaline batteries are manufactured in standardized cylindrical forms interchangeable with zinc-carbon batteries, and in button forms.
  • a cylindrical battery is contained in a drawn steel can, which is the cathode connection.
  • the positive electrode mixture is a compressed paste of manganese dioxide with carbon powder added for increased conductivity.
  • the paste may be pressed into the can or deposited as pre-molded rings.
  • the hollow center of the cathode is lined with a separator, a non-woven layer of cellulose (paper) or a synthetic polymer (plastic), which prevents contact of the electrode materials and short- circuiting of the cell.
  • the negative electrode is composed of a dispersion of zinc powder in a gel containing the potassium hydroxide electrolyte.
  • the central core of an alkaline button cell is the anode which is a dispersion of zinc oxide powder in a gel containing a potassium hydroxide electrolyte.
  • This core is surrounded by a separator which is a non-woven layer of cellulose (paper) or a synthetic polymer (plastic).
  • a separator which is a non-woven layer of cellulose (paper) or a synthetic polymer (plastic).
  • an annular cathode which is a compressed paste of manganese dioxide with carbon (graphite) powder to increase conductivity.
  • the anode, separator, and cathode are sealed in a drawn steel casing.
  • a method of recycling batteries is shown generally as 100 and includes an alkaline battery feed 102, a hammer mill 104, a degas station 106, an oven shown generally as 150, and a screener 126.
  • the method of recycling batteries 100 may also include a granulator 108, and a magnetic separator 132.
  • the alkaline battery feed 102 may include both spent and unspent alkaline batteries, both having the same chemical composition, but differing in moisture content. Unspent batteries contain more moisture than spent batteries.
  • the method of recycling batteries 100 includes the following steps:
  • Alkaline battery feed 102 is granulated by a hammer mill 104 and outputted as granulated feedstock 105.
  • the granulated feedstock 105 is smaller in size than the alkaline battery feed 102. Usually pieces do not exceed 1 3 ⁇ 4 inches, and normally are about 1 1 ⁇ 2 in size.
  • the granulated feedstock 105 is agglomerated which over time initiates a self-preheating process in the de-gas station shown generally as 106.
  • the minimum amount of agglomerated material was found to be about 200 pounds.
  • the agglomeration is brought about in a batch process where granulated feedstock 105 is placed in containers 109 for a preselected amount of time, typically in excess of twenty minutes.
  • agglomeration in this method could, alternatively, be brought about in a continuous process where granulated feedstock 105 is fed onto a moving container (i.e. a conveyor with upright side walls) for a preselected amount of time, typically in excess of twenty minutes.
  • a moving container i.e. a conveyor with upright side walls
  • the heat generated from self-heating is referred to as a preheating step at 152.
  • Energy in the form of heat from the preheating, step 152 is used to: encourage de-gassing in a de-gas step 154; partially dry the moisture from the granulated feedstock 105; and transfer heat via convention to ambient air 121 drawn into the de-gas station 106.
  • the de-gas step 154 extracts contaminant gases such as mercury gas. More specifically, the heat from the pre-heating step 152 volatilizes the mercury that may be present in the granulated feedstock 105 such that it can be extracted with negative pressure. Negative pressure draws air ambient air 121 through the granulated feedstock 105 flushing the mercury vapour, and other contaminant gases.
  • Ambient air 121 is also drawn through the feedstock to promote both drying and heat transfer to ambient air 121.
  • water vapour, mercury vapour and other gases including the ambient air 121, are heated and extracted from the de-gas station 106 in the form of heated ambient air 156.
  • the heated ambient air 156 is passed through a heat exchanger 140 which transfers heat to exterior air 141 drawn from outside the system.
  • the exterior air is heated and leaves the heat exchanger 140 as preheated exterior air 120.
  • Preheated exterior air 120 typically has a temperature exceeding of 250°F.
  • the heated ambient air 156 leaves the heat exchanger 140 and then enters an off-gas scrubber 142.
  • the off-gas scrubber 142 removes harmful contaminant gases and outputs clean off gas 144 as exhaust to the environment.
  • the preheated exterior air 120 is fed directly into the oven 150; and more specifically into the radiant tube heaters 116.
  • natural gas 122 may be added and combusted to raise the temperature further.
  • the granulated feedstock 105 leaving the de-gas station 106 may optionally be passed through the granulator 108 to further shred the granulated feedstock 105 into finely granulated feedstock 112.
  • the granulator 108 could be any means of fragmenting batteries; however, in this example it is a closed rotor granulator.
  • Finely granulated feedstock 112 is smaller in size than the granulated feedstock 10— usually, pieces do not exceed 3 ⁇ 4 inch.
  • the feedstock, granulated feedstock 105 or optionally finely granulated feedstock 112, is normally further heated in the oven 150 and outputted as dried feedstock 113. There may be instances in which further drying is not necessary.
  • the oven 150 having at least two conveyors 114 heats the feedstock via radiant tube heaters 116 and encloses the feedstock to receive residual off gas 124 via passive uptake vents. Residual off gas 124 travels to the off-gas scrubber 142 where it is processed and outputted as off gas 144.
  • At least two conveyors 114 are positioned at different heights to cascade the material, shown at 118 in Figure 1 and Figure 2. Specifically, feedstock is received by the higher of the conveyers 114 and allowed to fall onto the lower of the two conveyers 114. This cascade 118 promotes: i) separation of connected feedstock; ii) a more uniform stream of feedstock; and iii) further reduction of moisture from the feedstock.
  • the time during which the feedstock remains in the oven conveyor and the temperature of this conveyor are determined based on characteristics of the feedstock and desired properties of the powder output from the system. More specifically, a customer of the powder may specify a required dryness or mercury content for the powder. Characteristics of the feedstock which impact the required heating time and temperature are the size of the battery cells, the age of the cells (newer batteries need to be run slower at higher temperatures), mercury content, and the type of battery. Regardless of customer requirements, the feedstock must at least be sufficiently dry so that it separates at the screener 126.
  • the temperature of the oven can be varied as required, typically, a temperature of between a low temperature of 200°F and a high temperature of 600°F is sufficient where the feedstock remains in the oven conveyor for 1 to 10 minutes.
  • the speed of the conveyors determines the time in the oven conveyor. By way of example only one minute in the oven conveyor may correspond to a high speed whereas ten minutes in the oven conveyor may correspond to a low speed.
  • the preheating step 152 in the de-gas chamber 106 serves to reduce or at times eliminate the necessity of long oven times to dry the feedstock to dry the feedstock.
  • the granulated feedstock 105 leaves the oven 107 as dried feedstock 113 via the conveyors 114 and is screen separated by the screener 106 into a course fraction 127 and a powdered fraction 128.
  • the screener may be any commercially available screener (i.e. reciprocating, rotating, etc.); however, in this example it is a rotex screener.
  • the powdered fraction 128 represents 50-60% of the dried feedstock 113 and comprises zinc oxide, manganese dioxide and potassium hydroxide in proportions of 45-49%, 45-49%, and 2-10% respectively. Put another way, of the entire battery, zinc oxide represents 25-27%, manganese dioxide represents 25-27% and potassium hydroxide represents 3-5%.
  • This powdered fraction 128 is recovered as a finished product of the process.
  • the course faction 127 includes a magnetic portion 134 (i.e. metal from broken steel casing, brass, etc.) and a non-magnetic portion 136 (i.e. cellulose/ paper, plastic, etc.), which may optionally be separated via the magnetic separator 132 schematically represented in Figure 2.
  • a magnetic portion 134 i.e. metal from broken steel casing, brass, etc.
  • a non-magnetic portion 136 i.e. cellulose/ paper, plastic, etc.
  • the magnetic separator 132 having parallel spaced upper and lower conveyors receives course fraction 127 from the screener 126 on the lower of the two conveyors. A magnet above the underside of the upper conveyor, attracts the magnetic portion 134 to the underside of the upper conveyor.
  • the non-magnetic portion 136 remains on the lower conveyor to be deposited in a predetermined location; whereas, the magnetic portion 134 continues to travel on the underside of the upper conveyor, until it is sufficiently far from the magnet that the magnetic force is too weak to hold the magnetic portion 134 to the upper conveyor and the magnetic portion 134 is released to a predetermined location distinct from that corresponding to the non-magnetic portion 136.
  • the mesh size of the screen separator can be varied as required provided it is sufficiently small to separate the powder fraction of the feedstock. However, a #30 mesh size is suitable where the powder is to be used in the fertilizer industry and also allows the powder to pelletize well.

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  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Primary Cells (AREA)

Abstract

La présente invention concerne un procédé de récupération de composants constitutifs d'une matière première de batteries scellées comprenant : a) la granulation des batteries pour former une matière première granulée ; b) le préchauffage de la matière première par agglomération de la matière première granulée pour induire une réaction exothermique spontanée dans l'agglomérat de manière à auto-chauffer la matière première ; c) le chauffage plus avant de la matière première préchauffée avec une source de chaleur externe afin d'achever le séchage de la matière première ; d) la séparation par criblage de la matière première séchée en une fraction grossière et une fraction de poudre.
PCT/CA2016/051073 2015-09-11 2016-09-12 Recyclage de batteries Ceased WO2017041185A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562217147P 2015-09-11 2015-09-11
US62/217,147 2015-09-11

Publications (1)

Publication Number Publication Date
WO2017041185A1 true WO2017041185A1 (fr) 2017-03-16

Family

ID=58240458

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2016/051073 Ceased WO2017041185A1 (fr) 2015-09-11 2016-09-12 Recyclage de batteries

Country Status (1)

Country Link
WO (1) WO2017041185A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220152618A1 (en) * 2016-08-24 2022-05-19 Schäfer Elektrotechnik U. Sondermaschinen Gmbh Impact reactor
WO2023283685A1 (fr) * 2021-07-16 2023-01-19 Resource Conservation and Recycling Corporation Pty Ltd Procédé de récupération de valeurs à partir de batteries alcalines

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2311792A1 (fr) * 1998-09-28 2000-04-06 Mitsubishi Heavy Industries, Ltd. Procede de broyage de piles
CA2730320A1 (fr) * 2009-03-13 2010-09-16 Wayne C. Stevens Recyclage de batterie
CA2770727A1 (fr) * 2011-06-06 2012-12-06 Raw Materials Company Inc. Methode et systeme de recuperation d'elements constitutifs de batteries
US8734972B2 (en) * 2010-12-13 2014-05-27 Sumitomo Metal Mining Co., Ltd. Battery pack processing apparatus and processing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2311792A1 (fr) * 1998-09-28 2000-04-06 Mitsubishi Heavy Industries, Ltd. Procede de broyage de piles
CA2730320A1 (fr) * 2009-03-13 2010-09-16 Wayne C. Stevens Recyclage de batterie
US8734972B2 (en) * 2010-12-13 2014-05-27 Sumitomo Metal Mining Co., Ltd. Battery pack processing apparatus and processing method
CA2770727A1 (fr) * 2011-06-06 2012-12-06 Raw Materials Company Inc. Methode et systeme de recuperation d'elements constitutifs de batteries

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FRANCINE AMON ET AL.: "Fire risks associated with batteries''.", FIRE TECHNOLOGY, SP REPORT, 2012, pages 32 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220152618A1 (en) * 2016-08-24 2022-05-19 Schäfer Elektrotechnik U. Sondermaschinen Gmbh Impact reactor
US11975332B2 (en) * 2016-08-24 2024-05-07 Schäfer Elektrotechnik U. Sondermaschinen Gmbh Impact reactor
WO2023283685A1 (fr) * 2021-07-16 2023-01-19 Resource Conservation and Recycling Corporation Pty Ltd Procédé de récupération de valeurs à partir de batteries alcalines

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